Motor fuel composition

ABSTRACT

MOTOR FUEL COMPOSITION COMPRISING A MIXTURE OF HYDROCARBONS IN THE GASOLINE BOILING RANGE CONTAINING A NITROKETONIZED AMIDE CORRESPONDING TO THE FORMULA:   R-N(-R&#39;&#39;)-(CH2)3-NH-R&#34;   WHERE R, R&#39;&#39; OR R&#34; IS A NITRODETONIZED GROUP HAVING FROM 4 TO 40 CARBON ATOMS. THE NITROKETONIZED AMIDE PROVIDES THE FUEL COMPOSITION WITH SUCH PROPERTIES AS RUST PROTECTION, CARBURETOR DE-ICING AND CARBURETOR DETERGENCY.

United States Patent "ice 3,711,255 MGTQR FUEL COMPOSITION Donald R.Lachoviicz and George S. Saines, Fishkill, and George W. Eclrert,Wappingers Falls, N.Y., assignors to Texaco Inc., New York, N.Y. NoDrawing. Filed Dec. 24, 1970, Ser. No. 101,408 Int. Cl. (11011/18, 1/22US. Cl. 44-66 Claims ABSTRACT 0F THE DESCLDSURE Motor fuel compositioncomprising a mixture of hydrocarbons in the gasoline boiling rangecontaining a nitroketonized amide corresponding to the formula:

RNCHzCH2CH2-N-H I RI! Where R, R or R" is a nitroketonized group havingfrom 4 to 40 carbon atoms. The nitroketonized amide provides the fuelcomposition with such properties as rust protection, carburetor de-icingand carburetor detergency.

BACKGROUND on THE INVENTION This invention relates to an improved motorfuel composition for internal combustion engines. More particularly, theinvention involves the discovery that the incorporation of a minoramount of a nitroketonized amide into gasoline produces a fuel havingimproved carburetor detergent properties along with good corrosioninhibiting and anti-icing properties.

Modern internal combustion engine design is undergoing significantchanges to meet higher standards concerning engine and exhaust gasemissions. A major change in engine design presently being widelyadopted is the feeding of crankcase blow-by gases of the engine into theintake air supply to the carburetor rather than venting to theatmosphere as was done in the past. Blow-by gases, however, containsubstantial amounts of deposit-forming substances and it has beenobserved that some of the constituents in the blow-by gas form depositsin and around the throttle plate area of the carburetor. Such depositsrestrict the flow of air through the carburetor at idle and low speedsresulting in an overrich fuel mixture. Such a condition produces roughidling, engine stalling and also results in excessive hydrocarbonexhaust emissions to the atmosphere. In addition to overcoming theforegoing problem, a competitive modern gasoline must provide a highdegree of corrosion inhibiting and anti-icing properties.

A novel fuel composition has been discovered which mitigates orovercomes the problem of deposit laydown in the carburetor of aninternal combustion engine. More specifically, a motor fuel compositioncontaining a novel additive has been found which is effective forsubstantially reducing the laydown of deposits in a carburetor. Theadditive also provides excellent corrosion inhibiting and anti-icingproperties in the gasoline.

Broadly, this invention contemplates a motor fuel composition comprisinga mixture of hydrocarbons in the gasoline boiling range and a minoramount of a nitroketonized amide corresponding to the formula:

R-NCH.-CHaCH:N-H

g RI! where R is an alkyl, alkenyl, nitroketonized alkyl ornitroketonized alkenyl group, where R and R alternately representhydrogen and an alkanoyl, alkenoyl, nitroketonized alkanoyl ornitroketonized alkenoyl group, wherein at least one of said R, R or R"is a nitroketonized group as heretofore defined. In particular, R whenalkyl 3,711,255 Patented Jan. 16, 1973 represents a group having from 1to 40, preferably 8 to 22, carbon atoms and when alkenyl, nitroketonizedalkyl or nitroketonized alkenyl represents a group having from 4 to 40,preferably 8 to 22, carbon atoms. Further, R and R" when alternatelyrepresenting a group recited above, other than hydrogen, contains from 4to 40, preferably 8 to 22, carbon atoms.

The nitroketonized amides employed in this invention are prepared bycontacting the precursor, namely an acid amide, of the formula:

where R is an alkyl group having from 1 to 40 carbon atoms or alkenylgroup having from 4 to 40 carbon atoms, where R and R alternatelyrepresent hydrogen and an alkanoyl group or an alkenoyl group havingfrom 4 to 40 carbon atoms, wherein at least one of said R R or R is analkenyl or an alkenoyl group, with dinitrogen tetroxide and oxygen at atemperature of from about 35 to 45 C. in a mole ratio of said acid amideto dinitrogen tetroxide to oxygen of from 111:1 and 1:4:60. In adesirable embodiment R and R or R are respectively alkenyl and alkenoylgroups having from 4 to 40, preferably 8 to 22, carbon atoms and wherethe mole ratio of acid amide to dinitrogen tetroxide to oxygen is from1:2:2 to 1:4:60. Preferably, the reaction is conducted at temperaturesof from 10 to -30 C. and R R or R represent groups having from 8 to 22carbon atoms.

Nitroketonization of the aforementioned acid amide can be accomplishedin a one-step reaction as contrasted to other known processes whereolefins are initially converted to intermediate nitroperoxy compoundsand where the intermediate compound is subsequently contacted with adenitrating agent to yield a nitroketone product. Here, the introductionof a denitrating agent is not essential inasmuch as autogenousconversion at the point of unsaturation directly results in vicinalnitroketonization.

The acid amide containing at least one group identified as R R or Rpossessing at least one unsaturated group along a carbon chain isconverted in the course of nitroketonization to a vicinal nitroketonefunction For example, unsaturation of the acid amide may be in R as analkenyl group such as 3-buteny1, 2-pentenyl, IO-undecenyl, 9-octadecenyland l3-docosenyl. Alternatively R may be an alkyl group such as methyl,ethyl, butyl, hexyl, dodecyl, hexadecyl and tetracosanyl. When R isalkyl, unsaturation of the acid amide occurs at R or R as an alkenoylgroup such as 2-methyl-3-butenoyl, 3-butenoyl, IO-undecenoyl,S-hexadecenoyl, 9-octadenenoyl and 13-docosenoyl. Alternatively when Ror R is alkanoyl, such as isobutanoyl, heptanoyl, decanoyl,pentadecanoyl and tetracosanoyl, R is an alkenyl group. Forther,unsaturation may occur in a plurality of points along R R or R Moreover,unsaturation at one or more points may occur simultaneously in R and Ror R as when R is 9-octadecenyl and R or R is lO-undecenoyl. Dependingon the ratio of acid amide to dinitrogen tetroxide to oxygen, acidamides having a plurality of unsaturated linkages can to varying degreesbe singularly to totally converted to vicinal nitr'oketone groups. Wherea plurality of unsaturation occurs and it is contemplated that some orall be converted to vicinal nitroketone groups the lower ratios of acidamide to dinitrogen tetroxide to oxygen of 1:2:2 to 1:4:60 are employedalong with a denitrating agent introduced to the reaction product re- 3sulting from contacting of the acid amide, dinitrogen tetroxide andoxygen.

The denitrating agent is added to the reaction product in a mole ratioof agent to product of at least 1:1 and preferably less than about 20:1at a temperature about 35 to 45 C. Specific examples of denitratingagents include dimethylformamide, diethylformamide, dimethylacetamide,dirnethylsulfoxide, diethylsulfoxide, tetramethylurea andtetraethylurea.

When unsaturation of R R or R occurs internally, that is, on other thana terminal carbon atom, the reaction yields a mixture of two isomericvicinal nitroketonized amides, illustratively,N-(9-nitro-10-octadecanonyl)-N'- octadecanoyl-l,3-diaminopropane andN-(10-nitro-9-octadecanonyl)-N-octadecanoyl-1,3-diaminopropane. Whenunsaturation occurs between the terminal and adjacent carbon atom,nitration occurs on the terminal carbon and ketonization on the carbonvicinal thereto as for exampleN-decyl-N-(4nitro-3-butanonyl)-l,3-diaminoproane.

p The unsaturated acid amide employed as a starting reactant is preparedfrom readily available materials. Essentially, such an acid amide isprovided byreacting primary amine with acrylonitrile to yield thecorresponding N-(Z-cyanoethyl)-N-alkylamine and subsequently selectivelyhydrogenating the cyano group to the N-hydrocarbyl-1,3-diaminopropane (adiamine) where the hydrocarbyl radical is 'alkyl or alkenyl.Subsequently, the N- hydrocarbyl-1,3-diaminopropane is reacted with a Cto C alkanoic or alkenoic acid to form an ammonium salt of the acidwhich upon heating in the absence of added water is converted to theacid amide. With regard to the alkenyl or alkenoyl group, each may haveone or more points of unsaturation that subsequently undergonitroketonization according to the process herein described. Forexample, polyunsaturated acids as those occurring in whale oil, fishoil, corn oil, linseed oil and other oils can be employed including9,12-octadecadienoic acid and 9,12, -octadecatrienoic acid.

In the course of nitroketonization of the acid amide, air can beemployed as the source of oxygen or oxygen can be provided in admixturewith inert gases such as nitrogen or argon. Under preferred conditions,oxygen and dinitrogen tetroxide are respectively introduced into thereaction zone containing the amide at a rate of between 1 and 16milliliters per minute of oxygen per gram of amide and between about0.005 and 0.05 gram of dinitrogen tetroxide per minute per gram ofamide. Atmospheric and higher pressures may be employed and the reactionis conveniently conducted in the presence of inert organic solventshaving from 4 to 22 carbon atoms exemplified by hydrocarbons includingparaflins such as pentane, hexane, octane, decane, dodecane, octadecane;cycloparafiins such as cyclopentane and cyclohexane; and aromatichydrocarbons such as benzene and toluene. In general, reaction times ofabout one-half to ten hours are employed, the time related to the rateof addition of the dinitrogen tetroxide.

It is to be noted that the dinitrogen tetroxide employed is actually anequilibrium mixture of dinitrogen tetroxide and nitrogen dioxide withthe equilibrium being driven to essentially 100 percent dinitrogentetroxide at 0 C. and essentially 100 percent nitrogen dioxide at 140 C.at 1 atmosphere pressure.

Nitroketonized amides contemplated as motor fuel additives hereininclude by way of illustration and not limitation N-hexy1-N'-(9'-nitro-10-0ctadecanonoyl) -1,3-diaminopropane,

N-hexyl-N'- 10-nitro-9-octade-canonoyl) -1,3-diaminopropane,

N-hexyl-N-(9-nitro-lO-octadecanonoyl)-1,3-diaminopropane,

N-hexyl-N-( 1 0-.nitro-9-octadecanonoyl) 1, 3-diaminopropane,

N-(9"-n'itro-10-octadecanonyl)-N'-heptanoyl-1,3-diaminopropane,

N- 10-nitro-9-octadecanonyl)-N' heptanoyl-1,3-diaminopropane,

N-( 13-nitro-l4-docosanonyl)-N' (8-hexadecenoyl)- 1,3 -diaminopropane,

N-( l4-nitro- 13 -docosanonyl N- (-8-hexadecenoyl) 1,3-diaminoprop ane,

N-( l 3-docosenyl) -N'- 8-nitro-9-hexadecanonoyl) -1,3-

diaminopropane,

N- 13-docosenyl) -N(9-nitro-8-hexadecanonoyl) -1,3-

diaminopropane,

N-l3-nitro-14-docosanonyl)-N-(8-nitro-9-hexadecanonoyl)-1,3-diaminopropane,

N-( 14-nitrol 3-docosanonoyl) -N- 8-nitro-9-hexadecanonoyl 1,3-diaminopropane,

N-( l0-nitro-9-octadecanonyl) -N'--( 9-octadecenoyl 1,3-diaminopropane,

N(10-nitro-9-octadecanonyl)-N'-octanoyl-1,3-diaminopropane,

N- (Cg-C1 alkyl-N-( 10-nitro-9-octadecanonoyl) 1, 3-diaminopropane,

N-( 10-nitro-9-octadecanonyl) -N' l0-nitro-9-octadecanonoyl) -1,3-diaminopropane, and

N-(9-nitro-10-octadecanonyl)-N-(9-nitro10-octadecanonoyl) 1,3-diaminoprop ane.

In general, effective detergent motor fuels are produced by adding fromabout 0.0001 to 0.1 weight percent of the nitroketonized amide to thegasoline. A preferred concentration of the nitroketonized amide is inthe range from about 0.001 to 0.02 weight percent which corresponds toabout 3 to 60 p.t.b. (pounds of additive per 1000 barrels of fuel).

The carburetor detergency eifect of the additive and motor fuelscontaining the same was determined in a specially developed engine testdesignated the Chevrolet V8 Carburetor Detergency Test. This test wasconducted using a Chevrolet V8 engine equipped with a 4- barrelcarburetor mounted on a test stand. The two secondary barrels of thecarburetor were sealed and each of the primary barrels arranged so thatan additive fuel could be run in onebarrel and a base fuel run in theother. The primary carburetor barrels were modified to the extent thatthey had removable aluminum inserts in the throttle plate area so thatdeposits formed in this area could be conveniently weighed.

In the test designed to determine the effectiveness of thedetergent-containing fuel for preventing the lay-down of deposits, theengine is run for a period of 24 to 48 hours with the base fuel beingfed to one barrel and the additive fuel to the other barrel while engineblow-by is circulated to the air inlet of the carburetor. After the run,the inserts are removed from the carburetor and weighed to determine thedifference between the performance of the additive and non-additivefuels. The aluminum inserts are then cleaned, replaced in the carburetorand the process repeated with the fuels reversed in the carburetorbarrels to minimize differences in fuel distribution and barrelconstruction. The deposit weights in the two runs are averaged and thedetergency effectiveness of the additive fuel expressed in percent.

The anti-icing properties of the additive-containing fuel of theinvention was determined in a carburetor icing demonstrator apparatusconsisting of a vacuum pump equipped so that cool moisture-saturated airfrom an ice tower is drawn through a sample glass tube gasolinecarburetor. The gasoline sample is placed in a sample bottle and isdrawn into the glass carburetor through a 20 gage hypodermic needle.Evaporation of the gasoline in the gas tube further cools the cold moistair with resulting ice for mation on the throttle plate. The formationof ice on the throttle plate causes an engine to stall and it has beenfound that this condition is equivalent to a pressure drop across thethrottle plate of about 0.5 inch and 0.9 inch of mercury and the timerequired to reach this pressure drop is noted. The vacuum. pump isadjusted to give a vacuum of 1.8 inches of mercury and the test is rununtil either a pressure of 2.3 inches mercury has been reached or the 5run has continued for 300 seconds. Since, with most fuels, this pressuredrop is reached in l to 4 minutes 300 seconds is the maximum time for arun. A fuel composition which provides a minimum of 200 seconds run inthis test is an effective carburetor anti-icing fuel composition.

The anti-rusting propertiesof motor fuels was determined by insertingand thoroughly wetting a cold-rolled steel strip into a tall form fourounce glass bottle containing 90 cc. of the fuel sample and adding 20cc. of distilled water. The bottle was stoppered, agitated for 15seconds and stored at room temperature for 24 hours. The strip wasthereafter visually inspected and the percentage of rusted surface areaestimated.

In order to more fully illustrate the nature of this invention andmanner of practicing the same, the following examples are presented.

EXAMPLE I To a solution of 14.7 grams (0.025 mole) of a mixture ofN-(9-octadecenyl)-N'-(9-octadecenoyl) 1,3 diaminopropane and N-(9-octadecenyl) -N-(9-octadecenoyl) -1,3- diaminopropane in 200 ml. ofn-hexane as inert solvent, there was added simultaneously oxygen at arate of 60.8 milliliters per minute and dinitrogen tetroxide at the rateof 0.0081 mole per hour for 3.1 hours at C. After 3.1 hours, 1.5milliliters of liquid dinitrogen tetroxide (0.025 mole) had beentransferred to the reaction flask and the solution was purged withoxygen for about 1 hour. The reaction mixture was washed with 150 ml. of3.3% aqueous sodium bicarbonate and twice with 100 milliliters of waterand dried over sodium sulfate. Sodium sulfate was subsequently removedby filtration and the n-hexane was stripped by rotary evaporationleaving a product residue of 10.8 grams. Infrared spectroscopic analysisof the product obtained after nitrooxidation showed the presence of acarbonyl function and the absence of a peroxynitrate function and theproduct was identified as a mixture of nitroketotnized amides includingN- 10-nitro9-octadecanonyl) -N- 9-octadecenoyl) 1,3-diaminopropane,

N-( 10-nitro-9-octadecanonyl) -N (9-octadecenoyl)- 1,3-diaminopropane,

N 9-nitro- 10-octadecanonyl) -N- 9-octadecenoyl) 1,3-diaminopropane,

N- (9-nitro-10-octadecanonyl)-N-(9-octadecenoyl)- 1,3-diaminopropane,

N-(9-octadecenyl)-N'-(10-nitro-9-octadecanonoyl)- 1,3-diaminopropane,

N- (9-octadecenyl -N( l0-nitro-9-octadecanonoyl) 1,3-diaminopropane, 05

N-(9-octadecenyl) -N'-(9-nitro-10-octadecanonoyl)- 1,3-diaminopropaneand N-(9-octadecenyl) -N- (9-nitro-10-octadecanonoyl)-1,3-diaminopropane.

EXAMPLE II Example I was repeated employing 14.7 grams (0.025 mole) ofthe mixed acid amide with 200 ml. of toluene as the inert solvent andsimultaneously contacting the solution with oxygen introduced at therate of 60.8 milliliters per minute and dinitrogen tetroxide at the rateof 0.086 mole per minute for 2.9 hours. A product yield of 12.0 gramswas obtained and identified as a mixture of nitroketonized amides as inExample I.

EXAMPLE III To a solution of 25.5 grams (0.05 mole) ofN-(9-octadecenyl)-N-octanoyl 1,3 diaminopropane in 300 milliliters ofn-pentane as inert solvent, there was added simultaneously oxygen at therate of 60.8 milliliters per 6 minute and dinitrogen tetroxide at therate of 0.018 mole per hour for 2.75 hours at 0 C. After 2.75 hours 3.1ml. of liquid dinitrogen tetroxide (0.05 mole) had been transferred tothe reaction flask and the solution was purged with oxygen for about onehour. The solution was mixed with water forming an emulsion and pentanewas stripped under vacuum and replaced with ether. The aqueous layer wasseparated and the organic layer was washed three times with 100 ml.portions of water. The organic layer was dried over anhydrous sodiumsulfate, the latter removed by filtration and the solvent stripped fromthe product under vacuum. A yield of 12.9 grams of a product identifiedas a mixture of N-(l0-nitro-9-octadecanonyl)-N-octanoyl-l,3-diaminopropane andN-(9-nitro-10-octadecanonyl)-N'-octanoyl-1,3-diaminopropane wasrecovered.

EXAMPLE IV To a solution of 28.3 grams (0.05 mole) of N-(Calkyl-N'-(9-octadecenoyl) 1,3 diaminopropane in 300 milliliters ofcarbon tetrachloride as inert solvent, there was added simultaneouslyoxygen at the rate of 60.8 ml. per minute and dinitrogen tetroxide atthe rate of 0.015 mole per hour for 3.2 hours at 0 C. After 3.2 hours3.1 ml. of liquid dinitrogen tetroxide (0.05 mole) had been transferredto the reaction flask and the solution was purged with oxygen for aboutone hour. The reaction mixture was washed three times with 100 ml.portions of water. The organic layer was dried over anhydrous sodiumsulfate and the solvent was stripped from the product under vacuum. Ayield of 18.8 grams of a product identified as a mixture of N-(Calkyl-N-(10-nitro-9-octadecanonoyl)-1,3-diaminopropane and N-(C alkyl-N-(9-nitro-10-octadecanonoyl)-l,3-diaminopropane was recovered.

EXAMPLE V The base fuel employed in the following examples was a premiumgrade gasoline having a research octane number of about 101.5 containing3.0 cc. of tetraethyllead per gallon. This gasoline consisted of about25 percent aromatic hydrocarbons, 14.5 percent olefin hydrocarbons, 60.5percent parafiinic hydrocarbons and boiled in the range of about F. to380 F.

A gasoline blend was prepared consisting of the above base fuelcontaining 5 p.t.b. (pound per 1000 barrels of gasoline) of an acidamide mixture of N-(9-octadecenyl)-N-(9-octadecenoyl)-1,3-diaminopropane and N-(9-octadecenyl) N (9octadecenoyl) 1,3-diaminopropane. Another gasoline blend was preparedconsisting of the above base fuel containing 5 p.t.b. of thenitroketonized acid amide reaction product of Example I. The base fueland each of the additive-containing gasoline blends were tested andcompared for their carburetor detergency properties in the abovedescribed Chevrolet V-8 Carburetor Detergency Test. From the test, itwas determined that the gasoline blend containing the acid amideadditive mixture was 39 percent more effective than the base gasoline inpreventing the build-up of deposits in the carburetor. The gasolineblend containing the nitroketonized acid amide additive was 63 percentmore effective than the base gasoline in preventing the build-up ofdeposits in the carburetor.

EXAMPLE VI To a solution of 14.7 grams (0.025 mole) of a mixture of N (9octadecenyl)-N'- (9-octadecenoyl)l,3-diaminopropane and N (9octadecenyl) N (9-octadecenoyl)-l,3-diaminopropane in 200 ml. ofn-hexane as inert solvent, there was added simultaneously oxygen at arate of 60.8 milliliters per minute and dinitrogen tetroxide at the rateof 0.019 mole per hour for 2.7 hours at 0 C. After 2.7 hours, 3.0milliliters of liquid dinitrogen tetroxide (0.05 mole) had beentransferred to the reaction flask and the solution was purged withoxygen for one-half hour. Dimethylformamide (15 ml.) was added to thereaction solution dropwise over a period of 8 minutes at 2 to 5 C. Thesolution was mixed with 100 milliliters of 5 percent aqueous sodiumbicarbonate. Hexane was removed from the resulting mixture and replacedwith 400 milliliters of benzene. The aqueous phase was separated and thebenzene layer was washed three times with 200 milliliter portions ofwater. The benzene solution was dried over anhydrous sodium sulfate, thelatter removed by filtration and the solvent stripped from the productunder vacuum. A yield of 7.3 grams of a product composed of a mixture ofN( -nitro-9-octadecanonyl -N'( 10-nitro-9-octadecanonoyl)-1,3-diaminopropane,

N( 10-nitro-9-octadecanonyl -N-( 10-nitro-9- octadecanonoyl)-1,3-diamin0propane,

N( 10 nitro-9-octadecanonyl) -N-(9-nitro- 10'- octadecanonoyl1,3-diaminopropane,

N( 10-nitro-9-octadecanonyl) -N- (9-nitro-10-octadecanonoyl)-1,3-diaminopropane,

N- (9-nitro-l 0-octadecanonyl -N'-( 10-nitro-9- octadecanonoyl)-1,3-diaminopropane,

N- (9-nitro- 10-octadecanonyl) -N-( l0-nitro-9- octadecanonoyl1,3-diaminopropane,

N-(9-nitro-10-octadecan0nyl)-N-(9-nitro-1O-octadecanonoyl)-1,3-diaminopropane, and

N-(9-nitro-10-octadecanonyl) -N- (9-nitro-10-octadecanonoyl)-1,3-diaminopropane was obtained.

The base fuel employed in this example was a premium grade gasolinehaving a research octane number of about 102.0 containing 2.86 cc. oftetraethyllead per gallon. This gasoline consisted of about 34 percentaromatic hydrocarbons, 9 percent olefinic hydrocarbons, 57 percentparaffinic hydrocarbons and boiled in the range of about 90 F. to 380 F.A gasoline blend was prepared consisting of the base fuel containing 32p.t.b. of nitroketonized reaction product recited in Example VI. Thebase fuel and gasoline blend above were tested for the carburetorantiicing properties. The stalling time of base fuel at 0.5 inch ofmercury was 47 seconds and at 0.9 inch of mercury was 54 seconds. Thegasoline blend containing 32 pounds per thousand barrels of thenitroketonized reaction product at 0.5 inch of mercury was 260 secondsand at 0.9

inch of mercury was 274 seconds.

Another gasoline blend was prepared consisting of the above base fueland containing 32 p.t.b. of the nitroketonized acid amide of Example II.The stalling time of this gasoline blend at 0.5 inch of mercury was 231seconds and at 0.9 inch of mercury was 264 seconds.

The anti-rusting properties of the base fuel alone and 'base fuelscontaining 32 pounds per thousand barrels of the nitroketonized reactionproducts of Examples II and VI respectively were determined employingthe test procedure heretofore described. An examination of thecoldrolled steel strip contacted with the fuel layer in the base fuelrevealed that about 95 percent of the surface area had rusted. Incomparison, the base fuels containing respectively the nitroketonizedproducts of Examples II and VI showed zero percent rusting of thesurface area contacted with the fuel layer.

EXAMPLE VII The nitroketonized product of Example I was evaluated todetermine its affect, if any, on a motor fuels research octane atvarious concentrations with the results tabulated as follows.

Research octane number None (base gasoline) '101.5 Nitroketonized amide64 p.t.b 101.6 Nitroketonized amide 128 p.t.b 101.6 Nitroketonized amide256 p.t.b 101.5

From the tabulation it will be seen that even at high concentrations theadditive caused no significant change in octane number.

We claim:

1. A motor fuel composition comprising a mixture of hydrocarbons in thegasoline boiling range and from about 0.0001 to 0.1 weight percent of anitroketonized amide corresponding to the formula:

R-NCHzCHz-OHzN-H I Ru where R is an alkyl, alkenyl, vicinalnitroketonized alkyl or nitroketonized alkenyl group, where R and R"alternately represent hydrogen and an alkanoyl, alkenoyl, vicinalnitroketonized alkanoyl or vicinal nitroketonized alkenoyl group,wherein at least one of said R, R or 'R" is a nitroketonized group asheretofore defined.

2. A'motor fuel composition according to claim 1 containing from about0.001 to 0.02 weight percent of said nitro-ketonized amide.- 4 i 3. Amotor fuel composition according to-claim 1 where R when alkyl has from1 to 40 carbon atoms and when R is alkenyl, nitroketonized alkyl ornitroketonized alkenyl has from 4 to 40 carbon atoms and where R and R"when other than hydrogen represent a group having from .4 to 40 carbonatoms. p v p I 4. A motor fuel composition according to claim 1 where Rhas from 8 to 22 carbon atoms.

5. A motor fuel composition according to claim 1, where R or R" has from8 to 22 carbon atoms. 1

6. A motor fuel composition according to claim 1 wherein saidnitroketonized amide comprises N(lO-nitro- 9 octadecanonyl) N(9-octadecenoyl)-1,3-diaminopropane.

References Cited UNITED STATES PATENTS 1/ 1960 Lindstrom et al. 44-666/1968 Bouffard 44--72 X DANIELE. WYMAN, Primary Examiner WQJ. SHINE,Assistant Examiner

